Concurrent Stabilization of [pi]-Donor and [pi]-Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)2] Complexes

Aromatized cationic [(PNN)Re(πacid)(O)2]+ (1) and dearomatized neutral [(PNN*)Re(πacid)(O)2] (2) complexes (where πacid=CO (a), tBuNC (b), or (2,6-Me2)PhNC (c)), possessing both π-donor and π-acceptor ligands, have been synthesized and fully characterized. Reaction of [(PNN)Re(O)2]+ (4) with lithium...

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Bibliographic Details
Published in:Angewandte Chemie 2014-08, Vol.126 (32), p.8460
Main Authors: Mazzotta, Michael G, Pichaandi, Kothanda Rama, Fanwick, Phillip E, Abu-Omar, Mahdi M
Format: Article
Language:ger
Subjects:
Chemistry
Ligands
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Summary:Aromatized cationic [(PNN)Re(πacid)(O)2]+ (1) and dearomatized neutral [(PNN*)Re(πacid)(O)2] (2) complexes (where πacid=CO (a), tBuNC (b), or (2,6-Me2)PhNC (c)), possessing both π-donor and π-acceptor ligands, have been synthesized and fully characterized. Reaction of [(PNN)Re(O)2]+ (4) with lithiumhexamethyldisilazide (LiHMDS) yield the dearomatized [(PNN*)Re(O)2] (3). Complexes 1 and 2 are prepared from the reaction of 4 and 3, respectively, with CO or isocyanides. Single-crystal X-ray structures of 1a and 1b show the expected trans-dioxo structure, in which the oxo ligands occupy the axial positions and the π-acidic ligand occupies the equatorial plane in an overall octahedral geometry about the rhenium(V) center. DFT studies revealed the stability of complexes 1 and 2 arises from a π-backbonding interaction between the dxyorbital of rhenium, the πorbital of the oxo ligands, and the π*orbital of CO/isocyanide. [PUBLICATION ABSTRACT]
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201403788